Water-insoluble azo dyestuffs



Patented Oct. 22, 1940 UNITED STATES PATENT OFFICE 1 2,218,920 WATER-INSOLUBLE AZODYEST'UFFS I I Heinrich Morschel,

Leverkusen-Wiesdorf, and

Rudolf Bitter Wolfl, LeverkuseneKuppersteg, Germany, assignors to General Aniline'& Film Corporation, a, corporation of Delaware :N o Drawing. Application June 29, 1938, Serial I No. 216,486. In Germany July 6,1937

Claims. (01. 260-204) The present invention relates to new waterinsoluble. azo dyestuffs, to a: process of preparing the same and to fibers dyed with the said dyestuffs; moreparticularly it. relates to azo dyestuffs of the general formula:

In this formula It stands foralkyl, aryl, aralkyl or hydroaryl, 'Rrstands for the radical of an arylamideof an aromatic orthoh'ydroxycarboxylic acid, ,R, and B1 being free from waterv solubilizing groups, X and X1 stand for alkyl or alkoxy groups and'the residue'R;CO- is attached to one of the positions 3-or 4 with respect to the: azo bridge, Rinthe above general formula may be substituted e. g. by halogen, hydroxyl, alkoxy,

alkyl.

Our new dyestufisareobtainable by -coupling. the diazo compound oi ,an amineo-i the general formula: v

wherein R, X and XI-meanthe'same as stated aboveawith anaryl-amideof an aromatic. orthohydroxycarboxylic acid, whereby the components are selected in such a manner that they are free from watersolubilizing groups. The new dye- 0 groups inthe diazo component are especially valuable in .this respect For the. manufacture 0n. the fiber textiles oinatural or regenerated cellulose as well as those of animal fibers can be taken Eorflthe, 'manufacture of. the dyestufis various processes may be used, for example, the

minium chloride in the usual manner. ogous process, in which disubstituted anilines are converted into ketones, is described in U. S.

usual icecolour-process; of course, the diazo compounds mentioned can also be usedin stabilised form, for: instance, as nitrosamineor diazoamind-compounds. v I v H l V The diazo components used in the above described-process are obtainable e. g. by nitrating the correspondingly substituted ketones and reducing the nitro-compounds thus obtained, or by introducingtheicarboxylic acid radical into suitably substitutedkanilines according to the Friedel- Craft reaction-j f Dialkoxyacylbenzenes'are known, for'instance', from Beilstein, Handbuch" der' organischen Chemie, 14th .ed., Vol. VIII, pages 267-272 and 312-313, and Vol. VIII, first supplement, page 321. Into these compounds, an amino group is introduced, as istated above, by nitrating and .thenreducingthe nitro compound formed in. the

usual 'manner; The aminodialkoxy-benzenes employedin the second method stated for preparing the diazo componentsare, likewise,-known from Beilstein, Handbuch der organischen Chemie,"4th1ed., Vol. XIII, pages 780-785. These compounds are first converted into=the acetamino compounds (Beilstein, l c.) to protect the amino'group and then acted 'upon with alu An anal- Patent 2,078,538.

, w v The followmg'examples illustrate the mventlon without limiting it thereto.

Example 1 Well scoured, dried cottonware piece goods are slop-padded on a foulard with a solution, which contains per liter 15 gs of 1-(2'-hydroxynaph- 1 thalene- 3 *carboylamino) 2 -methoxy-4 -chlorobenzene, 22.5 cc. of sodium hydroxide solution, 34 B. and 22.5 cc. of Turkey-red oil.- The impregnated and. dried-materialds then passed through a developingesolution which I contains the diazo compound prepared from 13 gs. of 2.4-

dimethoxy-5-aminoacetophenone per liter and is weakly acetic. After a shortv passage through air the material is rinsed several times with cold water and finally soaped, rinsed and dried in the usual manner. r

A bluish-Bordeaux shade of very good fastness to peroxideis obtained.

Example 2 Well scoured, dried cotton yarn is impregnated with a solution of 4 gs. 1-(2'-hydroxynaphthalene-3'-carboy1amino) naphthalene, 10 cc. of so- 5 dium hydroxide solution 34 B. and cc. of Turkey-red oil 50% per liter, squeezed Well and developed with a weakly acetic developing-solution, which contains 3 gs. of 3-amino-2.5-dimeth- 10 oxybenzophenone as diazo compound per liter (obtained by nitrating and reducing 2.5-dimethoxybenzophenone) rinsed and soaped.

matic ortho-hydroxy-carboxylic acid derived from a member of the group consisting of naphthalene and carbazole, R and R1 being free from water-solubilizing groups, X and X1 stand for radicals of the group consisting of alkyl and al- 5 koxy, and the residue R.CO- is attached to one of the positions 3 and 4 with respect to the azo bridge, yielding when produced on the fiber various shades of good fastness properties.

2. As new products, watersolub-le azo dyestuffs 10 of the general formula:

alkoxy A Bordeaux shade of very good fastness propl erties is obtained. g l R,

For the sake of simplicity the further combina-- R C o tions are arranged in the following table: alkoxy Diazo component -Azo-component Shade 0 2,4-dimethoxy-fi-amino-acetophenone 1-metgyl-2-(2'-hydroxynaphthalene-3 carboylamino)-5'mcth- Bordeaux. oxy enzenc. D0 lugethoxy-Z-(2'-hydroxy-naphthalone-3-carb0ylan1in0);4-ch10r0- D0.

, enzene. Do 1, 3-dimeth0xy-4-(2-hydroxynaphthalene-3-car'h0y1ami110)-6- D chlor benzene. 2, 4-dimethoxy-5-amino-benzophenone 1, 4-dimcthoxy-2-(2-hydroxynaphtha1ene-3-carboylamino)-5- D0.

chlorobenzene. Do 1-(2-hydroxynapl tha1ene-3'-carboylamino)-naphthalene Sogmw at P1 11 BQ 25 V eaux. 2,4-dimethoxy-fi-amino-propriophenone 1-methoxy-2-(2-hydroxynaphtha1ene-3-carboylamino)-benzene. Bluish Bordeaux. Do 1-methyl-2-(2-11ydroxynaphthalene-3-carb0ylamin0)-benzene Reddish vi let. D0 l-Igethyl-2-methoxy-5-(2-hydroxy'naphthalene-3-carb0ylamin0) Bluish Borde xenzene. I 2, 4-dimeth0xy-5-amino-hexahydro-benzopheligathyl-Z-(2'-hydroxynaphthalene-S-carb0ylamin0)-5-meth0xy- Red Bordeaux, none. enzene; I I W I' 2, 4-diethoxy-5-amino-acetophenone 1, 4-dimeth0xy-2-(2-hydroxynaphtha1ene-3'-carb0ylamino)ben- Reddish Bordeaux. 30

zene. D0 1-(2'-hydroxynaphthalene-3-earboylamino)-naphthalene Bluish Bordeauxa -D0 i, 3-dimethoxyA-(2-hydroxynaphthalene-3'-carboylamino)-6- D0.

' ehlorobenzene'. 1 D0 l-(g;2-bcnzocarbazole-5"-hydroxy-4"-carboylamino)-4-1neth0xy- Reddishbluelack- Y enzene. I 2, 4-diethoxy-5-amin0-propriophenone 1, ZfiiimfihoxyA-(2-hydroxy-naphthalene-3'-carboy1amino)-6- Bordeaux. 35

c are enzene.'. 2, 4-dieth0xy-E-aminobenzophenone 1-(2!-hydroxynaphthalene-3-carboy1amino)-3-nitrobenzene- Staongly bluish, B P

. V v ,7 8mm I 3-amino-2,5-dimethoxy-acetophenone 1-methyl-2-(1, 2-benzocarbazole-5"-hydroxy-4" carboylamino)- Blulsh black 7 B-methoxybenzene. 1 D 1, gidimlethoxy i-Q-hydroxynaphthalene-3-carboy1amino)-6- Reddish vi let- 3 0 01'0 enzene. r 4O 3-amino-2,fi-dimethoxy-benzophenone lA-hdimethoxya-(2'-hydroxynaphthalene-8-carboylamino) -6- Bordeaux. v p c oro enzene.

Do l-methyl-2-(1,2-benzocarbazole-5"-hydroxy-4"-ca.rboyiamino)- 'Darkblue. E-methoxy-benzene. 3-am1n0-2,5-d1ethoxybenzophenone 1,3-hdimethoxy-4-(2-hydroxynaphthalene-3'-carboylamino)-6- Bluish Bordeaux.

' V c oro enzene. D0 1,4-dimethoxy-2- (2-hydroxynaphthalene-3' carboylamino) -5- Reddish Bordea I chlorobenzene. 4 5 4-ammo-2,5-d1methoxyacetophenone lfifiimethoxyi-(2'-hydroxynaphthalene-3'-carboylamino)-6 Currant. w

0 cm enzene. V 4-amino-2,5-dimethoxyptopriophenone l-Itnethoxy-2-(2-hydroxynaphthalene 3'-carboylamino)-4-chloro- Stongly bluish "UB0!- v enzene. eaux.

D 0 l-methyll-(2hydroxynaphtha1ene-3-catboy1amino)-benzene.. D0. 4-ammo-2,5-dimethoxyhexahydrobenzophe- 1-(2-hydroxynaphthalene-3-carboylamlno)-3-nitrobenzene Staongly bluish Bornone. ,7 eaux. Z-methoxyA-amino-5-methy1-acetopl1enone. l-metliyM-(2' hydroxynaphthalene-3'-carboylamino)-benzene Bluishred. D0 1-(2-hydroxynaphthalene-3-carboylaminc)-4-chlorobenzene. Yellowishted- D0 '1-1g1ethy1-2-(2'-hydrcxynaphthalene-3-carboylemino)-5-chloro- Red-Bordeauxenzene. 1,3- dimethoxyi- (2 -hydroxynaphthalene3' -carboylamino) -6- Bluish red.

chlorobenzene. 1,4 dimethoxy -2 (2 -hydroxynaphthalene -3 -carboylamino) -5- Yellowlsh red.

chlorobenzene. I 1 ijmethyl- -(2hydroxy-naphthalene-3-carboylamino)-5-chioro- Red.

enzene. 1 ngethoxy-Z-(2-hydroxy-naphthalene-S -carb0ylamino)-5-cl11o- Strongly yellowish red. r0 enzene. Y 4-amino-2.B-dimethyl-acetophenone 1, 4-diInethoxy-2-(2'-hydroxynaphthalene-3'-carboy1ami.no) ben- Bluish red.

Z8116. 1 Do 2-(2'-hydroxynaphthalene-3'-oarboylamino)-nap :lthalene Red. 0 2-methoxy-4-1nethyl-fi-amlnobenzophenone 2-hydroxynaphthalene-3-carboylaminobenzene Red-Bordeaux.

2.4-dimethoxy-5-ammo-phenylacetophenone l-methy1-2-(2-hydroxy-naphtha1ene-3-carboylamino)-benzene Blulsh garnet.

1- g ethyl-2(2-hydroxynaphthalene-3-carboylamino)-5-ch1orostronglybluishgarnet.

enzene. D0 1-(2hydroxynaphthalene-3-carboylamino)-naphthalene D0.

We claim:

1. As new products, water-insoluble azo dye stufis of the general formula:

R.CO

wherein R stands for a radical of the group consisting of alkyl, aryl, aralkyl and. hydroaryl, R1 75 stands for the radical of an arylamide of an ar0-' wherein R stands for a radical of the group con- 65 sisting of alkyl, aryl, aralkyl and hydroaryl, R1 stands for the radical 01 an arylamide of an arcmatic ortho-hydroxy-carboxylic acid derived from a member of the group consisting of naphthalene and carbazole, R and R1 being free from watersolub-ilizing groups, and the residue R.CO is attached to one of the positions 3 and 4 with respect to the am bridge, yielding when produced on the fiber various shades of good fastness prop-'- erties. 7

alkoxyQN=N-1h wherein R stands for a radical of the group consisting of alkyl, aryl, aralkyl and hydroaryl, R1 stands for the radical of an arylamide of an arcmatic ortho-hydroxy-carboxylic acid derived from a member of the group consisting of naphthalene and carbazole, R and R1 being free from watersolubilizing groups, yielding when produced on the fiber various shades of good fastness properties.

4. As a new product the water-insoluble azo dyestufl of the formula HCI) (i70.NH

CHaO N=N CH:

yielding when produced on the fiber Bordeaux shades of good fastness properties.

5. As a new product the water-insoluble azo dyestufi of the formula:

I ?CH:

yielding when produced on the fiber bluish Bordeaux shades of good fastness properties.

6. Fibers dyed with a dyestuff as claimed in claim 1.

7. Fibers dyed with a dyestuff as claimed in claim 2.

8. Fibers dyed with a dyestufl as claimed in claim 3.

9. Fibers dyed with a dyestuff as claimed in claim 4.

:10. Fibers dyed with a dyestufi as claimed in claim 5.

HEINRICH MORSCHEL. RUDOLF RI'I'IER WOLFE. 

